MXPA02008053A

MXPA02008053A - Powdered thermosetting composition for coatings.

Info

Publication number: MXPA02008053A
Application number: MXPA02008053A
Authority: MX
Inventors: Luc Moens
Original assignee: Ucb Sa
Priority date: 2000-12-21
Filing date: 2001-12-17
Publication date: 2003-01-28
Also published as: CN1208412C; WO2002050201A1; JP2004516357A; CN1404517A; US20050136186A1; AU2002231714A1; EP1358287A1; KR20020079880A; US20030166793A1; CA2400576A1; TW593595B

Abstract

The present invention relates to powdered thermosetting compositions including a binder which comprises a carboxyl group containing amorphous isophthalic acid containing polyester, a carboxyl group containing aliphatic semi-crystalline polyester, an optional and different carboxyl group containing semi-crystalline polyester, at least 5 parts by weight, based on the total weight of the binder, of a specific glycidyl group containing acrylic copolymer and a curing agent having functional groups reactive with the polyesters carboxyl groups. The powdered thermosetting compositions are useful for the preparation of powdered paints and varnishes which give semi-matt coatings having an outstanding flow, a remarkable weatherability and excellent mechanical properties.

Description

THERMOSTABLE COMPOSITION IN POWDER FOR COATINGS DESCRIPTION OF? INVENTION The present invention relates to thermosetting powder compositions comprising as a binder a mixture of particles capable of reacting together of an amorphous polyester containing carboxyl groups, a semi-crystalline aliphatic polyester containing carboxyl groups, an acrylic copolymer containing glycidyl groups and a curing agent containing β-hydroxyalkylamide groups whose functional groups are reactive with the carboxyl groups of the polyesters. Optionally, the compositions may contain another semicrystalline polyester containing carboxyl groups. The invention also relates to the use of said compositions for the preparation of paints and powder varnishes which produce semi-matt coatings which provide extraordinary creep, excellent weather resistance and excellent mechanical properties. The invention is further related to the semi-matt coatings obtainable from said compositions. Thermosetting powder compositions are widely used as paints and varnishes for coating REF: 141085 of the majority of various articles. These powders have many advantages. On the one hand the problems associated with solvents are completely eliminated and on the other hand the powders are not wasted, since only the powder in direct contact with the article is retained in the article, being in principle, recoverable and reusable, any powder in excess. For these and other reasons, powder coating compositions are preferred to coating compositions in the form of solutions for example in organic solvents. Powder coating compositions should give coatings which have good adhesion to metal substrates such as steel or aluminum, a good flow without defects and rough surface, good flexibility and weather resistance as well as good chemical resistance. Also, powder coating compositions should exhibit a glass transition temperature high enough to avoid re-agglomeration during handling, transportation and storage. Most current coating compositions provide coatings that have a high gloss after melting and curing. In fact, the brightness measured at a 60 ° angle according to the ASTM D523 method is often equal or in fact greater than 90%. For example, WO 97/20895 describes compositions thermosetting powders including a binder consisting of a mixture of semicritaline and amorphous polyesters containing carboxyl groups, and a cross-linking agent with functional groups capable of reacting with the carboxyl groups of the polyesters. Powder thermosetting compositions are useful for the preparation of powder coatings and paints and provide coatings having excellent weather resistance, high gloss and excellent mechanical properties. WO 91/14745 discloses a thermosetting powder coating composition comprising as a binder a mixture of particles capable of reacting together a semicrystalline polyester component of carboxylic acid function and a curing agent having groups reactive with the carboxylic acid groups. If desired, the composition may include an amorphous polyester, which is said to provide coatings with improved weather resistance performance and improved resistance to coating gloss reduction during outdoor exposure. The powder coating compositions termed "hybrids" comprise an epoxy resin as a curing agent capable of reacting as a whole. Acrylic polyglycidyl polymers are mentioned among numerous other resins epoxies The coatings obtained from these thermosetting powder compositions have a high gloss. Although powder compositions are known to provide high gloss coatings with good appearance and mechanical properties as well as good weather resistance, there is an increasing demand for paints and powder varnishes that provide matt or semi-matt coatings of good quality, for example to coat certain accessories in the automotive industry, such as wheel rims, bumpers and the like, or for the coating of panels metallic and beams used in construction. Therefore, several methods have been proposed for the manufacture of paints and powder varnishes that provide matte or semi-matt coatings. According to one of these methods, one or more agents are introduced that provide a matt coloration, as described in US 4,242,253, in the powder composition, in addition to the conventional binder and pigments. US 3,842,035 relates to a curing powder composition with curing ability, which upon curing provides a matte finish and which comprises a mixture of a thermostable, slow curing and fast curing powder composition. The two compositions are extruded separately before the dry combination. WO 92/01756 discloses powder coating compositions comprising one or more semicrystalline hydroxyl polyesters, one or more amorphous polyesters and one or more hydroxyl acrylic polymers and an inactivated polyisocyanate crosslinking agent. The coatings of the compositions in shaped metal articles have a gloss value of ASTM D-523-85 at 60 ° not greater than 35. EP-A-0 551 064 discloses thermosetting powder compositions comprising as a binder a mixture of a linear carboxyl group containing polyester and a glycidyl group containing acrylic copolymer. The acrylic polymer should have a number of molecular weight (Mn) of 4000 to 10000 in order to obtain coatings with useful physical properties. The compositions are useful for the preparation of paints and varnishes in powder that produce matte finishes with a gloss value measured at an angle of 60 ° in accordance with the ASTM D523 method equal to or less than 15. Despite the existing variability of methods for the production of matte or semi-matt finishes, experience has shown that all these methods are subject to one or more disadvantages attributed to processing problems, as well as to the overall behavior of the coating. The problems relate in particular to the reproducibility and reliability of the brightness value. Therefore there is a need for thermosetting powdered compositions, capable of producing semi-matt coatings which do not show the defects and disadvantages of the prior art. In addition there is a sustained effort to improve the flexibility and weather resistance of the semi-matt finish in order to make it suitable for applications such as coil coatings, for example intended for outdoor construction purposes, especially for use in regions that have a climate tropical. However, when semi-matured finishes are considered, there is currently no known method for the preparation of thermoset powder compositions from a single extrusion, which, when cured, provides criteria such as extra-ordinary fluence, outstanding and excellent weather resistance. flexibility and for which low brightness values are observed in a reproducible and reliable way. In accordance with the present invention, it has surprisingly now been found that by using as a binder a mixture of particles capable of reacting together from a polyester containing isophthalic acid with of carboxyl groups, semi-crystalline aliphatic polyester containing carboxyl groups, optionally another semicrystalline polyester containing carboxyl groups, at least 5 parts by weight of an acrylic copolymer containing specific glycidyl groups and a curing agent containing β-hydroxyalkylamide groups with functional groups Reagents with the carboxyl groups of the polyesters, it is possible to obtain thermosetting powdered compositions which produce coatings having the desired characteristics. Thus, in accordance with the present invention there is provided a thermosetting powder composition comprising a binder comprising (a) an amorphous polyester containing isophthalic acid containing carboxyl groups, (b) a semicrystalline aliphatic polyester containing carboxyl groups, (c) optionally a semicrystalline polyester other than (b), containing carboxyl groups, (d) at least 5 parts by weight, based on the total weight of the binder, of an acrylic copolymer containing glycidyl groups, said copolymer comprising minus 10 mol% of a monomer containing glycidyl groups and having a number of expected molecular weight (Mn) of 10000 or less, and (e) a curing agent containing * .beta.-hydroxyalkylatiid groups whose functional groups are reactive with the carboxyl groups of the polyesters. The present composition is useful for the preparation of coatings with semi-matt coloration, that is, coatings having a gloss value, measured at an angle of 60 ° according to the ASTM D523 method, between 20 and 80. In the sense of the present application the term "polyester containing isophthalic acid" refers to to a polyester which is composed of at least 10 mol% isophthalic acid, preferably at least 50 mol% based on the total acid constituents of the polyester. The amorphous polyester and semi-crystalline polyesters can be independently linear or branched. The amorphous polyester (a) containing carboxyl groups of the present composition is preferably composed, with reference to the acidic constituents, of 10 to 100 mol% isophthalic acid, preferably 50 to 100 mol%, and 90 to 0 mol% of another diacid, such as an aliphatic, cycloaliphatic or aromatic diacid, and, with reference to the alcoholic constituents, from 35 to 100 mol% of neopentyl glycol and / or 2-butyl-2-ethyl-1, 3-propanediol and of 65 to 0% mol from another diol, such as an aliphatic or cycloaliphatic diol. The branching of the amorphous polyester can be obtained by the incorporation of a polyacid or a polyol. The acidic constituent of the amorphous polyester, which is not isophthalic acid, can preferably be selected from one or more aliphatic, cycloaliphatic or aromatic diacids, such as fumaric acid, maleic acid, phthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane-dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, etc., or the ahydrides corresponding. The incorporation for example of up to 15 mol% in relation to the diacid, of polyacids having at least three carboxylic acid groups such as trimellitic acid or pyromellitic acid or their corresponding anhydrides or their mixtures, induces the branching of the polyester. The glycolic constituent of the amorphous polyester, which is not neopentyl glycol and / or 2-butyl-2-ethyl-l, 3-propanediol, can be preferably selected from one or more aliphatic or cycloaliphatic glycols, such as ethylene glycol, propylene glycol, , 4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 't t * li 1Jauá ^ - ** ^ - * ^ 2-methyl-l, 3-propanediol, hydrogenated Bisphenol A, neopentyl glycol hydroxypivalate, etc. The incorporation for example of up to 15 mol% in relation to neopentyl glycol and / or 2-butyl-2-ethyl-1,3-propanediol, of trifunctional or tetrafunctional polyols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol or their mixtures, induces the polyester branch. The amorphous polyesters (a) containing carboxyl groups of the present composition preferably have an acid number (AN) of 15 to 70 mg KOH / g and in particular 20 to 50 mg KOH / g. Amorphous polyesters containing carboxylic groups are further advantageously characterized by: a number of expected molecular weight (Mn) in the range of 1600 to 11000 and preferably 2200 to 5600, as measured by gel permeation chromatography (GPC). a vitreous transition temperature (Tg) of 40 to 80 ° C, measured by Differential Scanning Calorimetry according to the method ASTM D3418 with a heating gradient of 20 ° C per minute; and an ICI viscosity (cone / plate) according to ASTM method D4287-88, measured at 200 ° C in the range of 5 to 15,000 mPa.s. * tfMbír? lñmu? Mi * ~ -, D ~? M, t ^ ' The amorphous polyester containing carboxyl groups can meet one or more of the above conditions for their acid number, their average molecular weight number, their vitreous transition temperature and their ICI viscosity. However, preferably, the amorphous polyester meets all these requirements. The semi-crystalline aliphatic polyester of carboxylic function (b) is composed with reference to the acid constituents, from 40 to 100 mol% of a straight chain dicarboxylic acid containing from 10 to 16 carbon atoms and from 0 to 60 mol% of the minus a straight chain dicarboxylic acid containing from 4 to 9 carbon atoms. The alcoholic constituents of the semi-crystalline aliphatic polyester of carboxylic function (b) is selected from at least one unbranched or cycloaliphatic aliphatic diol containing from 2 to 16 carbon atoms. The straight chain dicarboxylic acid containing from 10 to 16 carbon atoms of the semi-crystalline aliphatic polyester of carboxylic function (b) is selected from 1,10-decanedioic acid, 1,1-undecanedioic acid, 1,2-dodecanedioic acid, 1, 13-triadecanedioic acid, 1,4-tetradecanedioic acid, 1,1-pentadecanedioic acid, 1,1-hexadecanedioic acid, used in a mixture or alone. The straight chain dicarboxylic acid containing 4 to 9 carbon atoms of the semicrystalline aliphatic polyester of carboxylic function (b) is selected from succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid. The unbranched or cycloaliphatic aliphatic diol containing 2 to 16 carbon atoms of the semi-crystalline aliphatic polyester of carboxylic function (b) is selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, 12-dodecanediol, 1, 14-tetradecanediol, 1,16-hexadecanediol or 1, 4 -cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated Bisphenol A, 2,2,4,4-tetramethyl-l-3-cyclobutanediol or 4,8-bis (hydroxymethyl) tricyclo [5.2.1. O2'6] dean, used in a mixture or alone. The second semicrystalline polyester of carboxylic function (c), optionally used in the formulation of the present invention, is composed of 75 to 100 mol% of terephthalic acid and / or 1,4-cyclohexanedicarboxylic acid and / or straight chain dicarboxylic acid it contains from 4 to 9 carbon atoms and from 25 to 0 mol% of another aliphatic, cycloaliphatic or aromatic diacid. The alcoholic constituent of the second semicrystalline polyester of carboxylic function (c), optionally used in the formulation of the present invention, is composed of from 75 to 100 mol% of a cycloaliphatic diol or of linear chain containing from 2 to 16 carbon atoms and from 25 to 0 mol% of another aliphatic glycol. The straight chain dicarboxylic acid containing from 4 to 9 carbon atoms of the optional second semicrystalline polyester of carboxylic function (c) is selected from succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid and azelaic acid, used in a mixture or alone, and 25 to 0 mol% of the other aliphatic, cycloaliphatic or aromatic diacid is selected from fumaric acid, maleic anhydride, phthalic anhydride, isophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, used in a mixture or alone. The cycloaliphatic or straight-chain diol containing 2 to 16 carbon atoms of the optional second semicrystalline polyester of carboxylic function (c) is selected from ethylene glycol, 1,3-propanediol, 1-butanediol, 1,5-pentanediol, 1 , 6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1,12-dodecanediol, 1, 14-tetradecanediol, 1, 16-hexadecanediol or 1, 4 -cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated Bisphenol A, 2, 2, 4, 4-tetramethyl-l, 3-cyclobutanediol or 4,8-bis (hydroxymethyl) tricyclo [5.2.1. O2'6] decane, used as a mixture or alone, and 25 to 0 mol% of the other aliphatic glycol is selected from propylene glycol, neopentyl glycol, 2-methyl-l, 3-propanediol, 2-butyl-2-ethyl- l, 3-propanediol, neopentyl glycol hydroxypivalate, used alone or mixed. Both semicrystalline polyesters of carboxylic function (b) and (c) of the present invention can be linear or remelted. When branching is required, incorporation of up to 15 mol%, based on the total diacids, of polyacids having at least three carboxylic acid groups, such as pyromellitic acid or trimellitic acid or their corresponding anhydrides or up to 15% can be effected. mol based on the amount of diols, trifunctional or tetrafunctional polyols such as trimethylolpropane, di-trimethylolpropane, pentaerythritol or mixtures thereof. The semi-crystalline carboxylic functional polyesters (b) and (c) of the present invention have an acid number (AN) of 10 to 50 mg KOH / g and preferably 20 to 40 mg KOH / g. Additionally they are characterized by: an average molecular weight number (Mn) in the range of 2200 to 17000 and preferably 2800 to 8500; a melting zone of 30 to 150 ° C, as measured by Differential Scanning Calorimetry (DSC) according to ASTM method D3418 with a heating gradient of 20 ° C per minute; a vitreous transition temperature (Tg) of -50 to + 50 ° C, as measured by Differential Scanning Calorimetry (DSC) according to the method ASTM D3418 with a heating gradient of 20 ° C per minute; - a degree of crystallinity, measured by Differential Scanning Calorimetry (DSC) according to the method ASTM D3415 of at least 5 J / g and preferably at least 10 J / g; an ICI viscosity (cone / plate) according to ASTM method D4287-88, measured at 175 ° C in the range of 5 to 20,000 mPa.s. Both semicrystalline polyesters (b) and (c) containing carboxyl groups can meet one or more of the above conditions for acid number, average molecular weight number, melting zone, vitreous transition temperature, degree of crystallinity and the ICI viscosity. However, preferably, the semicrystalline polyesters meet all the above requirements. The acrylic copolymer (d) containing glycidyl groups of the present composition is preferably composed of from 10 to 90 mol% of a monomer containing glycidyl groups and from 90 to 10 mol% of other monomers copolymerizable with the monomer containing glycidyl groups. t *, ^ ,,, ^, ^^,.,. i ^. ^^ A ^ The glycidyl group-containing monomer used in the acrylic copolymer of the present composition may be selected, for example, glycidyl acrylate, glycidyl methacrylate, methyl glycidyl methacrylate., methyl glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meta) acrylate and acrylic glycidyl ether. These monomers can be used alone or in combination of two or more. The other monomers of the acrylic copolymer copolymerizable with the glycidyl group containing monomer can be selected from: 40 to 100 mole percent of acrylic ester or methacrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate , n-butyl acrylate, n-decyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-methacrylate, -hexyl, isoamyl methacrylate, acrylic methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methacrylate 2-et? lbutyl, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate, cyclopentyl methacrylate, methacrylate methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-phenylethyl methacrylate and phenyl methacrylate.

Or to 60 mol percent of other copolymerizable unsaturated monomers such as styrene, substituted alkyl styrenes and substituted chloro styrenes, acrylonitrile, vinyl chloride, vinylidene fluoride and vinyl acetate. The acrylic copolymers containing glycidyl groups of the present composition preferably have an epoxide equivalent weight of 1.0 to 7.0 and preferably 1.5 to 5.0 milliequivalents of epoxide / gram of polymer. The acrylic copolymers containing glycidyl groups can be further characterized by: a number average molecular weight (Mn) in the range of 1000 to 10000, as measured by gel permeation chromatography (GPC); a vitreous transition temperature (Tg) of 40 to 85 ° C, as measured by Differential Scanning Calorimetry (DSC), according to ASTM method D3418 with a heating gradient of 20 ° C per minute; - an ICI viscosity (cone / plate) determined by the ICI method at 200 ° C in the range of 50 to 50000 mPa.s. The acrylic copolymer containing glycidyl groups can meet one or more of the above conditions for their epoxide equivalent weight, their average molecular weight number, their vitreous transition temperature and their ICI viscosity. However, preferably the acrylic copolymer meets all the above requirements. The curing agent (e) according to the present invention, having functional groups reactive with the carboxylic groups of the polyesters is a β-hydroxyalkylamide. The β-hydroxyalkylamides, preferably used in the present invention, correspond to the general structure represented in Formula I.

Where: A represents a mono or polyvalent group derived from a saturated or unsaturated alkyl group with 1 to 60 carbon atoms, or an aryl group, or a trialkene amino group with 1 to 4 carbon atoms per alkylene group, or a group carboxy-alkenyl, or a carbonyl-alkenyl alkoxide. R 1 represents hydrogen, an alkyl group with 1 to 5 carbon atoms or a hydroxy alkyl group with 1 to 5 carbon atoms.

R2 and R3 are the same or are different and each independently represents hydrogen or a linear or branched alkyl group with 1 to 5 carbon atoms, while the R2 groups and one of the R3 groups may also form, together with the carbon atoms. adjacent carbon, a cycloalkyl group. Preferably, the β-hydroxyalkylamide is according to the following Formula II: Where n is between 0.2 and about 1, and R3 is a hydrogen (Primid XL552 from EMS) or a methyl group (Primid QM1260 from EMS). The amorphous polyester containing carboxylic groups and the semi-crystalline polyesters containing carboxylic groups of the present composition can be prepared using conventional esterification techniques well known in the art. The polyesters are prepared according to a process consisting of one or more reaction steps.

For the preparation of these polyesters, a conventional reactor equipped with a stirrer, an inert gas inlet (nitrogen), a thermocouple, a distillation column connected to a water-cooled condenser, a water separator and a water tube can be used. vacuum connection. The esterification conditions used to prepare the polyesters are conventional, that is, a standard esterification catalyst, such as dibutyltin oxide, dibutyltin dilaurate, n-butyltin trioctoate, sulfuric acid or sulfonic acid, can be used in an amount of 0.05 to 1.50% by weight of the reactants and optionally, color stabilizers can be added, for example, phenolic antioxidants such as Irganox 1010 (Ciba) or phosphonite and phosphite type stabilizers such as tributylphosphite, in an amount of 0 to 1% by weight of the reactants. The polyesterification is generally carried out at a temperature which is gradually increased from 130 ° C to about 190 to 250 ° C, first at normal pressure, then, when necessary, at reduced pressure at the end of each stage of the process, at the time these operating conditions are maintained until a polyester is obtained, which possesses the desired hydroxyl number and / or acid number. Then follows the degree of esterification ^ * j¿ ^ jfc by determining the amount of water formed in the course of the reaction and the properties of the obtained polyester, for example the hydroxyl number, the acid number, the molecular weight or the viscosity. When the polyesterification is complete, cross-linking catalysts can optionally be added to the polyester when it is still in the molten state. These catalysts are added in order to accelerate the cross-linking of the thermoset powder composition during curing. Examples of such catalysts include (e.g., 2-phenylimidazoline), phosphines (e.g., triphenylphosphine), ammonium salts (e.g., tetrabutylammonium bromide or tetrapropylammonium chloride), phosphonium salts (e.g., ethyltriphenylphosphonium bromide or tetrapropylphosphonium chloride). ). These catalysts are preferably used in an amount of 0 to 5% based on the weight of the polyester. The acrylic copolymer containing glycidyl groups can be prepared by conventional polymerization techniques, either in bulk, in emulsion, or in solution in an organic solvent. The nature of the solvent has very little importance, as long as it is inert and easily dissolves the monomers and the synthesized copolymer. Suitable solvents include toluene, ethyl acetate, butyl acetate, xylene, etc. The monomers are copolymerized in the presence of a free radical polymerization initiator (benzoyl peroxide, dibutyl peroxide, azo-bis-isobutyronitrile, and the like) in an amount representing 0.1 to 4.0% by weight of the monomers. In order to achieve a good control of the molecular weight and its distribution, a chain transfer agent, preferably of the mercaptanic type, such as n-dodecyl mercaptan, t-dodecanetiol, iso-octylmercaptan, or of the type, is also added during the reaction. carbon halide, such as carbon tetrabromide, bromotrichloromethane, etc. The chain transfer agent is used in amounts of up to 10% by weight of the monomers used in the copolymerization. Generally, a double-walled cylindrical reactor equipped with a stirrer, a condenser, an inert gas (eg, nitrogen), inlet and outlet systems and pumping feed is used to prepare the acrylic copolymer containing glycidyl groups. The polymerization can be carried out under conventional conditions. Therefore, when, for example, the polymerization is carried out in solution, an organic solvent is introduced into the reactor and heated to a temperature refluxing under an atmosphere of inert gas (nitrogen, carbon dioxide, and the like) and subsequently when required a homogeneous mixture of the required monomers, a free radical polymerization initiator and an anti-scavenging agent are gradually added to the solvent over several hours. chain transfer. Subsequently the reaction mixture is maintained at the indicated temperature for a few hours, while stirring. The obtained copolymer is subsequently freed from the solvent in vacuo. Preferably, the binder system of the thermosetting powder composition of the present invention comprises, based on the total weight of the binder: 20 to 89.5, preferably 30 to 70 parts by weight of the amorphous polyester containing isophthalic acid containing carboxyl groups ( a), 5 to 50, preferably 5 to 30 parts by weight of the semicrystalline aliphatic polyester containing carboxylic groups (b), 0 to 50, preferably 5 to 30 parts by weight of the semi-crystalline polyester containing carboxylic groups (c); 5 to 40, preferably 5 to 25 parts by weight of the acrylic copolymer containing glycidyl groups (d), and 0.5 to 10.0, preferably 1 to 5 parts by weight of the β-hydroxyalkylamide curing agent (e).

The binder system of the thermosetting composition of the present invention is preferably composed in a way that for each equivalent carboxyl group present in the amorphous polyester (a) and semicrystalline polyesters (b) and (c) are between 0.3 and 2.0 and preferably between 0.6 and 1.7 equivalents of epoxide groups of the acrylic copolymer (d) and between 0.2 and 1.2 and preferably between 0.4 and 1.0 equivalents of reactive functional groups of the ß-hydroxyalkylamide curing agent (e). The combination of thermoset polyesters (a, b and c), when required, can be obtained by dry blending of the amorphous polyesterés and semicrystalline polymers using a mechanical mixing process available for premixing the powder paint constituents. Alternatively the amorphous and semi-crystalline polyesters can be combined in the melt using a conventional cylindrical double-walled reactor or by extrusion such as with Betol BTS40. In addition to the essential components described above, the compositions within the scope of the present invention may also include one or more additives such as catalysts, fillers, control agents, creep such as Resiflow PV5 (Worlee), Modaflow (Monsanto), Acronal 4F (BASF), etc., and degassing agents such as benzoin (BASF), etc. UV light absorbers such as Tinuvin 900 (Ciba), hindered amine light stabilizers represented by Tinuvin 144 (Ciba), other stabilizing agents such as Tinuvin 312 and 1130 (Ciba), antioxidants such as Irganox 1010 can be added to the formulation. (Ciba) and phosphonite or phosphite type stabilizers. Both pigmented systems can be prepared as well as clear lacquers. A variety of dyes and pigments may be used in the composition of the present invention. Examples of useful pigments and dyes are metal oxides such as titanium dioxide, iron dioxide, zinc oxide and the like, metal hydroxides, metal powders, sulfides, sulfates, carbonates, silicates, such as ammonium silicate, carbon black, Talc, China clay, barite, ferric blue, lead blue, organic red, organic chestnut and the like. The components of the composition according to the invention can be mixed by dry blending in a mixer or stirrer (e.g., drum mixer). Subsequently the premix is homogenized at temperatures in the range of 70 to 150 ° C in an extruder of M. ^^^. ^? ^ M ^ MMM ^ c a single screw such as BUSS-Ko-Kneter or a twin screw extruder such as PRISM or APV. The extrudate, when cooled, is ground to a powder with a particle size preferably in the range of 10 to 150 μm. The powder composition can be deposited on the substrate by means of a powder gun such as a CORONA electrostatic gun or TRIBO gun. On the other hand well-known powder deposition methods such as the fluidized bed technique can be used. After depositing the powder, it is heated to a temperature between 160 and 320 ° C, causing the particles to flow and melt together to form a smooth, uniform, continuous coating with no crater-like points on the surface of the substrate. Therefore, the present invention is further related to the use of the compositions described above as powder varnishes or paints or for the preparation of a powder coating or paint. The invention is further related to powder coatings or paints that consist of, or comprise the present thermoset powder composition. Additionally, the present invention relates to a method of preparing a coating on a substrate comprising the steps of applying the varnish ? * t ~ or aforementioned paint to the substrate and heating the coated substrate to melt and cure the varnish or powder paint to obtain the coating. In addition, the present invention also relates to a coating that can be prepared by the above method and to a substrate completely or partially coated with that coating. The following examples are presented for a better understanding of the invention but are not intended to restrict the invention to them.

EXAMPLES If not specified otherwise, all quantities are given in parts by weight. In addition to the abbreviations already defined above, OHN refers to the hydroxyl number and Tm refers to the fusion zone. Example 1: Synthesis of a stage of an amorphous polyester of carboxylic function. 423.4 parts of neopentyl glycol are placed in a conventional four-neck round bottom flask equipped with a stirrer, a distillation column connected to a water-cooled condenser, an inlet for nitrogen and a thermocouple coupled to a thermoregulator. ± ?? ^. **? ^ * »» * - •. ~ * 4 »*? ^. ¿^ * ^ .i * tlt? Ti» * ^ mém The contents of the flask * are heated, while stirring under a nitrogen atmosphere, at a temperature close to 130 ° C at which point 719.6 parts of isophthalic acid and 2.5 parts of n-butyltin trioctoate are added. The heating continues gradually until a temperature of 230 ° C. Water is distilled from the reactor from 180 ° C. When the distillation at atmospheric pressure is stopped, a vacuum of 50 mm Hg is gradually applied. After three hours at 230 ° C and 50 Hg, the following are obtained characteristics: AN 34 mg KOH / g OHN 3 mg KOH / g ICI 200 ° C (cone plate) 2100 mPa.s Tg (DSC, 20 ° / min) 60 ° C 15 Example 2: Synthesis in two stages of an amorphous polyester of carboxylic function 424.87 parts of neopentyl glycol are placed in a conventional four-neck round bottom flask as in Example 1. The contents of the flask of the heater, while stirring under a nitrogen atmosphere, at a temperature close to at 130 ° C at which point 324.0 parts of terephthalic acid and 285.9 parts of isophthalic acid and 2.2 parts are added of n-butyltin trioctoate. Continuous heating gradually to a temperature of 230 ° C. Water is distilled from the reactor from 180 ° C. When the distillation is stopped at atmospheric pressure, a vacuum of 50 mm Hg is gradually applied. After three hours at 230 ° C and 50 mm Hg, the following characteristics are obtained: AN 9 mg of KOH / g OHN 57 mg of KOH / g 111.3 parts of isophthalic acid are added to the prepolymer of the first stage which has 200 ° C. Subsequently, the mixture is gradually heated to 230 ° C. After a period of 2 hours at 230 ° C and when the reaction mixture is clear, a vacuum of 50 mm Hg is gradually applied. After 3 hours at 230 ° C, the following characteristics are obtained: AN 31 mg KOH / g OHN 3 mg KOH / g ICI 200 ° C (cone plate) 4400 mPa.s Tg (DSC, 20 ° / min) 54 ° C Examples 3 to 5 According to the procedure described in example 1, the amorphous polyesters of example 3 and example 4 are prepared. Example 5 is prepared according to the procedure used in example 2. In a first In this step, a prepolymer of terephthalic acid-neopentyl glycol with a hydroxyl number of 50 mg KOH / g. The hydroxyl functional prepolymer is placed inside the reactor with isophthalic acid to obtain an amorphous polyester having a carboxylic function with an acid number of 30 mg KOH / g.

Table 1 Examples 6 to 9: Synthesis of semi-crystalline polyesters of carboxylic function. The two polyesters of Examples 6 and 7 whose composition and properties are given in Table 2, are semi-crystalline aliphatic polyesters of carboxylic function (b), according to the invention. Both polyesters of examples 8 and 9 are semicrystalline polyesters of carboxylic function (c), whose presence is optional in the thermosetting powder compositions according to the invention.

Table 2 The semi-crystalline carboxy functional polyesters of Examples 6 to 8 are prepared in accordance with Tul ii ii mriiiiiiM rtiiiifiíüMit? Tíjj¿ | Example 1. The semi-crystalline polyesters of carboxylic function of Example 9 are prepared according to the procedure of Example 2 wherein isophthalic acid is reacted with a prepolymer based on terephthalic acid-1,6-hexanediol with a hydroxyl number of 40. mg of KOH / g. Example 10 Preparation of acrylic copolymer containing glycidyl groups. 800 parts of n-butyl acetate are carried in a 5 liter double-walled flask equipped with a stirrer, a water-cooled condenser, a nitrogen inlet and a thermocouple coupled to a thermoregulator. The contents of the flask are subsequently heated and stirred continuously while purging nitrogen through the solvent. At a temperature of 125 ° C, a mixture of 38.5 parts of tert-butyl peroxybenzoate in 200 parts of n-butyl acetate is fed into a flask for 215 minutes with a peristaltic pump. 5 minutes after this starts another pump starts with feeding a mixture of 132 parts of styrene, 585 parts of glycidyl methacrylate, 123 parts of butyl methacrylate and 160 parts of methyl methacrylate, for 180 minutes. The synthesis is carried out in 315 minutes.

- Iil ii iliil ii tiíiiljgi ^ After evaporation of the n-butyl acetate an acrylic copolymer with the following characteristics is obtained: ICI viscosity @ 200 ° C 3500 mPa.s Mn 5800 Example 11 to 13 According to the procedure described in example 10, the Acrylic copolymers of Example 11 to Example 13, corresponding to the compositions of Table 3. Table 3 Example 14 The polyesters and acrylic copolymers illustrated above are subsequently formulated with a powder according to one of the formulations mentioned below. "•" ^ • "^ ÉilHii .Maftinmn Mipiinniiririltinii Formulation A Formulation B White paint formulation Paint formulation Coffee Binder 74.00 Binder 78.33 Kronos 2310 24.67 Bayferrox 130 4.44 Resiflow PV5 0.99 Bayferrox 3950 13.80 Benzoin 0.34 Black Smoke FW2 1.09 Resiflow PV5 0.99 Benzoin 0.35 The composition of the binders are given in Table 4, where binders 1 to 3 are in accordance with the invention and binders 4 to 6 are comparative. Table 4 * Binders 4 to 6 are comparative For the preparation of the powder formulation the amorphous polyester resin rich in isophthalic acid of carboxylic function and the semicrystalline polyester resins of carboxylic function can be used as a combination or as separate resins. When used as a combination, the combination is carried out by mixing the respective resins in the molten state using a conventional round bottom flask. The powders are first prepared by the dry combination of the different components and then by homogenization in the melt using a PRISM twin screw extruder of 16 mm L / D of 15/1 and an extrusion temperature of 85 ° C. . The homogenized mixture is subsequently cooled and crushed in an Alpine UPZ100. Subsequently the powder is screened to obtain a particle size between 10 and 110 μm. The powder obtained in this way is deposited on cold rolled steel, by means of electrostatic deposit using the GEMA - Volstatic PCG 1 spray gun. With a film thickness between 50 and 80 μm the panels are transferred to an air-ventilated oven , where curing takes place for 18 minutes at a temperature of 200 ° C. The characteristics of the paint for the finished coatings obtained from formulation A (example 15 to 33) and formulation B (examples 34 to 37) with GFi? ifws binder ions as specified in table 4, are reproduced in table 5. In this table, example 29 is given to example 33 of comparative examples. Table 5 m? ímíj ^ jk Table 5 (continued) Examples 29 to 33 are comparative In this table: Column 1: indicates the identification number of the formulation. Column 2: indicates the composition of the binder. Column 3: indicates the type of amorphous polyester (a). Column 4: indicates the type and% by weight of the semicrystalline aliphatic polyester (b) in the sum of polyesters (b) + (c). Column 5: indicates the type and% by weight of the semicrystalline polyester optionally used according to the invention, in the sum of the polyesters (b) + (c). Column 6: indicates the type of acrylic copolymer (d). Column 7: indicates the brightness at 60 °, measured according to the method ASTM D523 Column 8: indicates the direct impact resistance according to the method ASTM D2794. The greatest impact to which the coating does not fracture is recorded in Kg.cm. Column 9: indicates the resistance to the reverse impact according to the method ASTM D2794. The greatest impact to which the coating does not fracture is recorded in Kg.cm. For all the coatings obtained from the different formulations (according to the invention as well as for those of the comparative examples), a smooth visual perception was perceived, free of any defect. liliIttíiÉilltliiiiitpiMiÉr - "- ^ --- - ^^ - ^ - ^^^ - ^ - ^^ - ^^^^ * ^^. ^ - ^^^^^. ^^^^ ¿^^^ - ^ In addition, the different coatings of the formulations according to the invention (examples 15 to 28), all have a flexibility of OT or maximum IT, in accordance with the bending test T of the method ASTM D4145-83. For the comparative examples (examples 29 to 33), bending values T equal to or greater than 2T were observed. As can be seen clearly from table 5, the semicrystalline aliphatic polyester containing linear aliphatic C 10 -C 16 dicarboxylic acids is necessary to have coatings that provide a reduced gloss (example 16 against example 30 and example 19 against example 29). By changing the type of linear aliphatic dicarboxylic acid a modified gloss level is obtained (example 17 against example 20). It is also observed that increasing the amount of the semicrystalline aliphatic polyester containing linear aliphatic C 10 -C 16 dicarboxylic acids in the binder composition induces a proportional reduction in gloss of the coated derivative (example 15 to example 18, example 21 against example 22). , example 23 against example 24, example 25 against example 26). Also, it is appreciated that by increasing the amount of terephthalic acid in the carboxyl-functional amorphous polyester, within the preferred range of the present .t ^ ,, .. í ****. ^. ^^^ invention, has no influence on the properties with regard to brightness and flexibility. The increase in the content of terephthalic acid up to a proportion where it becomes predominant with respect to the content of isophthalic acid, influences the brightness and flexibility (example 17 against example 23 against example 28). The increase in weight equivalent to acrylic has an influence on the gloss and flexibility of the derived paint film (example 26 versus example 27). The presence of the ß-hydroxyalkylamide hardener is necessary to obtain a paint film showing flexibility (example 17 against example 31). The replacement of the β-hydroxyalkylamide hardener by a glycidyl group-containing hardener, well known in the art, such as triglycidyl isocyanurate (TGIC), has no influence on the level of gloss, but greatly reduces the flexibility of the paint (example 17 against example 32). The replacement of the hardening system of the present invention (acrylic copolymer containing glycidyl and β-hydroxyalkylamide) by a hardener generally used in commercial powder coatings intended for outdoor applications, such as isocyanurate fc? j ^^ i ^ jl ^ jji ^ i ^ jm t mÉ m Mmi triglycidyl, results in coatings that exhibit a total lack of flexibility (example 17 versus example 33). From all these examples it is clear that to obtain a flexible coating of low gloss or semi-matt coloration from the formulation obtained in a simple extrusion process, the powder formulation must necessarily comprise: an amorphous polyester containing functional isophthalic acid carboxylic acid, from which the acid constituent comprises at least 10 mol% isophthalic acid and preferably 50 mol% isophthalic acid; a semi-crystalline aliphatic polyester of carboxylic function, derived from linear chain C10-C16 aliphatic dicarboxylic acids, preferably in combination with another semi-crystalline polyester of carboxylic function; an acrylic copolymer containing glycidyl groups to react with the carboxylic acid groups of the polyester; - a cross-linking agent containing β-hydroxyalkylamide groups. In addition, all coatings in accordance with the present invention demonstrate that they meet excellent outdoor resistance, in comparison or better than powders commercially available today and normally used. In table 6, the values of brightness relative to 60 °, registered every 400 hours, according to the method ASTM D523, are reported for the coating obtained from examples 34 and 35, subjected to the resistance test to the weathering accelerated by Q-UV. In the same table (comparison) there are results of exposure to the weather of a carboxylic acid amorphous polyester obtained by reaction of 400.6 parts of neopentyl glycol, 22.3 parts of trimethylolpropane and 724.7 parts of isophthalic acid, in the same way as in Example 3. This polyester has an AN of 32 mg KOH / g and a Tg of 59 ° C, determined by DSC with a heating interval of 20 ° C / min. This polyester is formulated in a ratio of 93/7 with PT810 according to the formulation of the brown paint as in formulation B. In this table only reductions of brightness up to 50% of the maximum value are mentioned. The outdoor exposure measurements are carried out in a very harsh environment, ie the apparatus for weathering tests accelerated by Q-UV (Q-panel Co) according to the ASTM G53-88 method (practical standard for the operation of the apparatus of exposure to light and water - UV type Ititárf pt lÉHii-tiiili • íiiiriMflÉiftir r ^^ * - »'^ - ^ * nmiíi - * - * ^^' fluorescent / condensation - for exposure of non-metallic materials). For this table, the coated panels have been subjected to the intermittent effects of condensation (4 hours at 50 ° C) as well as to the damaging effects of simulated sunlight by UV-A fluorescent lamps (340 nm, 1 = 0.77 W / m2 / nm) (8 hours at 60 ° C). Table 6 dA ± Á? ¿? m¿ ^. ~ * - - - ^ - ^^^ - **** M? * C.

Table 6 (continued) It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. biA ifaá Bafc1 |. | t n, r i | ff 'rtigín-

Claims

CLAIMS Having described the invention as above, the content of the following claims is claimed as property. A powder thermosetting composition characterized in that it includes a binder comprising: (a) an amorphous polyester containing isophthalic acid which contains carboxyl groups, (b) a semicrystalline aliphatic polyester containing carboxyl groups, (c) optionally, a polyester semicrystalline other than (b) containing carboxylic groups. (d) at least 5 parts by weight, based on the total weight of the binder, of an acrylic copolymer containing glycidyl groups, the copolymer comprises at least 10 mol% of a monomer containing glycidyl groups and has an average molecular weight number (Mn) of 10000 or less, and (e) a curing agent containing β-hydroxyalkylamide groups whose functional groups are reactive with the carboxylic groups of the polyesters.
2. A composition in accordance with the ?. *. s .... ^. ,,. * ^ ... A ^ ^. ^^^^ ^^ Jtu claim 1, characterized in that the amorphous polyester (a) containing isoprene acid containing carboxylic groups consists of 10-100 mole% isophthalic acid and 0-90 mole% other diacid, based on the total of the acidic constituents , and from 35-100 mol% of neopentyl glycol and / or 2-butyl-2-ethyl-l, 3-propanediol and from 0-65 mol% of another diol, based on the total alcoholic constituents.
3. The composition according to claim 1, characterized in that the amorphous polyester containing isophthalic acid containing carboxylic groups additionally contains up to 15 mol% of polyacids in relation to diacids and / or up to 15 mol% of polyols, in relation to neopentyl glycol and / or 2-butyl-2-ethyl-l, 3-propanediol.
4. The composition according to any of claims 1 to 3, characterized in that the amorphous polyester (a) containing isophthalic acid containing carboxylic groups has an acid number (AN) of 15-70 mg KOH / g, a average molecular weight number (Mn) from 1600 to 11000, a vitreous transition temperature of 40-80 ° C and an ICI viscosity (cone / plate) at 200 ° C of 5-15000 mPa.s.
5. The composition according to any of claims 1 to 4, characterized in that the semicrystalline aliphatic polyester (b) containing carboxylic groups consists of 40 to 100 mol% of straight chain dicarboxylic acid containing from 10 to 16 carbon atoms and from 0-60 mol% of at least one straight chain dicarboxylic acid containing from 4 to 9 carbon atoms, based on the total of the acidic constituents, and at least one unbranched or cycloaliphatic aliphatic diol containing from 2 to 16 carbon atoms, as the alcoholic constituent.
6. The composition according to any of claims 1 to 5, characterized in that the optional semicrystalline polyester (c) containing carboxylic groups consists of 75-100 mol% of 1,4-cyclodextricarboxylic acid and / or terephthalic acid and / or straight chain dicarboxylic acid containing from 4 to 9 carbon atoms, and from 0-25 mol% of another aliphatic, cycloaliphatic or aromatic diacid, based on the total of the acidic constituents, and 75-100 mol% of a cycloaliphatic or straight-chain diol containing from 2 to 16 carbon atoms and 0-25 mol% of another aliphatic diol, based on the total of the alcoholic constituents.
The composition according to claims 5 to 6, characterized in that the semicrystalline polyesters (b) and (c) containing carboxylic groups additionally contain up to 15 mol% of polyacids in with 1,4-cyclohexanedicarboxylic acid and / or terephthalic acid and / or straight chain dicarboxylic acid, and / or up to 15 mol% polyols, in relation to the diols.
A composition according to any of the preceding claims, characterized in that both semicrystalline polyesters (b) and (c) containing carboxylic groups have an acid number (AN) of 10-50 mg KOH / g, a number average molecular weight (Mn) of 2200-17000, a melting zone of 30-150 ° C, a glass transition temperature (Tg) of -50 to 50 ° C, a degree of crystallinity of at least 5 J / g and an ICI viscosity (cone / plate) at 175 ° C of 5-20000 mPa.s.
9. A composition according to any of the preceding claims, characterized in that the acrylic copolymer containing glycidyl groups consists of 10-90 mol% of a monomer containing glycidyl groups selected from the group consisting of glycidyl acrylate, glycidyl methacrylate , methyl glycidyl acrylate, methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, glycidyl ether acrylic and mixtures thereof and 10-90 mole% monomers copolymerizable with the glycidyl group containing monomers
10. A composition according to any of the preceding claims, characterized in that the lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll A ^ Mi Acrylic copolymer containing glycidyl groups has an epoxide equivalent weight of 1.0 to 7.0 milliequivalents of epoxide / gram of polymer, a number average molecular weight (Mn) in the range of 1000 to 10000, a glass transition temperature (Tg) of 40-85 ° C and an ICI viscosity (cone / plate) at 200 ° C of 60-50000 mPa.s.
11. A composition according to any of the preceding claims, characterized in that the binder comprises, based on the total weight of the binder, (a) 20 to 89.5 parts by weight of amorphous polyester containing isophthalic acid which contains carboxyl groups, (b) 5 to 50 parts by weight of the semicrystalline aliphatic polyester containing carboxylic groups, (c) 0 to 50 parts by weight of the semi-crystalline polyester containing carboxylic groups other than (b); (d) 5 to 40 parts by weight of the acrylic copolymer containing glycidyl groups, and (e) 0.5 to 10.0 parts by weight of the curing agent containing β-hydroxyalkylamide groups.
The composition according to any of the preceding claims, characterized in that it additionally comprises one or more additives selected from the group consisting of catalysts, fillers, agents i'liilMriii - 'itrtiiin? -nü íi? n? fftr? iirm ??? rítr? tff? ii '^ - - * ^^ - ^ - ^^^ - ^ - > of flow control, degassing agents, UV light absorbers, light stabilizers, antioxidants and other stabilizers.
The composition according to any of the preceding claims, characterized in that it additionally comprises one or more dyes and / or pigments, such as metal oxides, metal hydroxides, metal powders, sulfides, sulfates, carbonates, silicates, carbon black, talc , china ds clay, barite, ferric blue, lead blue, organic reds and organic chestnut.
14. A method of preparing a composition according to any of claims 1-13, characterized in that it comprises the steps of combining the components of the composition to prepare a premix, homogenization of the premix at a high temperature such as 70- 150 ° C and crushing the homogenized product to obtain the thermosetting powder composition.
15. The method according to claim 14, characterized in that in a first stage the amorphous polyester and semi-crystalline polyesters are combined dry or combined by melting.
16. The use of a composition according to any of claims 1-13, characterized because its use is like a varnish or powder paint or for the preparation of a varnish or powder paint.
17. Varnish or powder coating characterized in that it consists of or comprises a composition according to any of claims 1-13.
18. A method of preparing a coating on a substrate characterized in that it comprises the steps of applying varnish or powder paint according to claim 17 to the substrate and heating the coated substrate to melt and cure the varnish or powder coating to obtain the coating.
19. A coating, characterized in that it can be prepared by the method according to claim 18.
20. A substrate coated in its entirety or partially characterized according to claim 19. "'l li lllli ll' fii'iiM I